Hydroamination iron catalyst

G. A. Khger, L. S. Glebov, R. A. Fridman, E. I. Bogolepova, and A. N. Bashkirov [Kinet. Catal., 19, 489 (1978)] studied the kinetics of the hydroamination of 2-octanone and other aliphatic ketones over a sintered iron catalyst ... 

Ruthenium and iron compounds have been claimed to catalyze the hydroamination of olefins with NH3, primary and secondary amines (120-190°C, 10-20 bar) [113, 114]. Ethylene is the most reactive olefin either with ruthenium (Eq. 4.11) or with iron catalysts (Eq. 4.12). 

Iron salts (e.g. FeCls) have been identified as new catalysts for intramolecular hydroamination. A number of olefinic tosylamides underwent the reaction at 80 °C to form the corresponding the N-tosylpyrrolidine derivatives in good yield.63 The same salt can also catalyse Markovnikov addition of electron-rich arenes and heteroarenes to styrenes, giving rise to 1,1-diarylalkanes at 80 °C.64... 

The aziridination of olefins, which forms a three-membered nitrogen heterocycle, is one important nitrene transfer reaction. Aziridination shows an advantage over the more classic olefin hydroamination reaction in some syntheses because the three-membered ring that is formed can be further modified. More recently, intramolecular amidation and intermolecular amination of C-H bonds into new C-N bonds has been developed with various metal catalysts. When compared with conventional substitution or nucleophilic addition routes, the direct formation of C-N bonds from C-H bonds reduces the number of synthetic steps and improves overall efficiency.2 After early work on iron, manganese, and copper,6 Muller, Dauban, Dodd, Du Bois, and others developed different dirhodium carboxylate catalyst systems that catalyze C-N bond formation starting from nitrene precursors,7 while Che studied a ruthenium porphyrin catalyst system extensively.8 The rhodium and ruthenium systems are... 

Iron pentacarbonyl and some ruthenium(III) complexes, such as RuCls 3 H2O or Ru(NH3)4(OH)Cl2, are claimed in a patent as catalysts for the hydroamination of ethylene and higher olefins in homogeneous solution [13]. 

---